Photoemission investigations on nanostructured TiO2 grown by cluster assembling

Nanostructured titanium dioxide (ns-TiO₂) films were grown by supersonic cluster beam deposition method. Transmission electron microscopy demonstrated that films are mainly composed by TiO₂ nanocrystals embedded in an amorphous TiO₂ phase while their electronic structure was studied by photoemission spectroscopy. The cluster assembled ns-TiO₂ films are expected to exhibit several structural and chemical defects owing to the large surface to volume ratio of the deposited clusters. Ultraviolet photoemission spectra (hv = 50 eV) from the valence band unveil the presence of a restrained amount of surface Ti 3d defect states in the band gap, whereas Ti 2p core level X-ray photoelectron (hv = 630 eV) spectra do not manifestly disclose these defects.     

An investigation into ultra-thin pseudobinary oxide (TiO<Subscript>2</Subscript>)<Subscript>x</Subscript>(Al<Subscript>2</Subscript>O<Subscript>3</Subscript>)<Subscript>1-x</Subscript> films as high-<Emphasis Type="Italic">k</Emphasis> gate dielectrics

As potential gate dielectric materials, pseudobinary oxide (TiO₂)_x(Al₂O₃)_1-x (0.1≤x≤0.6) films (TAO) were deposited on Si (100) substrates by pulsed-laser deposition method and studied systematically via various measurements. By a special deposition process, including two separate steps, the TAO films were deposited in the form of two layers. The first layer was deposited at room temperature and the second layer was completed at the substrate temperature of 400 °C. Detailed data show that the properties of the TAO films are closely related to the ratio between TiO₂ and Al₂O₃. The existence of the first layer deposited at room temperature can effectively restrain the formation of the interfacial layer. And according to the results of X-ray photoelectron spectroscopy and high-resolution transmission electron microscopy performed on the films, no other information belonging to the silicon oxide could be observed. For the (TiO₂)_0.4(Al₂O₃)_0.6 film, the best result has been achieved among all samples and its dielectric constant is evaluated to be about 38. It is valuable for the amorphous TAO film as one of the promising dielectric materials for high-k gate dielectric applications. PACS 77.55.+f; 73.40.Qv; 81.15.Fg     

Nanostructured TiO<Subscript>2</Subscript> Films with a Mixed Phase for Perovskite Solar Cells

A series of thin films made with TiO₂ nanoparticles with a varied anatase/rutile phase ratio is prepared on conducting glass substrates using a spin-coating method. The structure, morphology, and optical properties of TiO₂ nanopowders and thin films fabricated are studied using powder X-ray diffraction, scanning electron microscopy, and optical spectroscopy. The TiO₂ nanostructured films created are used as photoelectrodes for the fabrication of perovskite solar cells (PSCs). The photovoltaic characteristics of PSCs under AM1.5 light illumination (1000 W/m²) under ambient conditions are studied. It is shown that the best efficiency of solar-to-electrical energy conversion, namely, 9.3%, is obtained for the PSC with a photoelectrode based on a TiO₂ film with an anatase/rutile mixed phase ratio of 86/14%.     

Antibacterial effect of silver modified TiO<Subscript>2</Subscript>/PECVD films

This paper deals with photocatalytic activity of silver treated TiO₂ films. The TiO₂ films were deposited on glass substrates by plasma enhanced chemical vapor deposition (PECVD) in a vacuum reactor with radio frequency (RF) low temperature plasma discharge in the mixture of oxygen and titanium isopropoxide vapors (TTIP). The depositions were performed under different deposition conditions. Subsequently, the surface of TiO₂ films was modified by deposition of silver nanoparticles. Photocatalytic activity of both silver modified and unmodified TiO₂ films was determined by decomposition of the model organic matter (acid orange 7). Selected TiO₂ samples were used for tests of antibacterial activity. These tests were performed on Gram-negative bacteria Escherichia coli. The results clearly proved that presence of silver clusters resulted in enhancement of the photocatalytic activity, which was up to four times higher than that for pure TiO₂ films.     

Poly(vinyl chloride)-<Emphasis Type="Italic">graft</Emphasis>-poly(<Emphasis Type="Italic">N</Emphasis>-vinyl caprolactam) graft copolymer: synthesis and use as template for porous TiO<Subscript>2</Subscript> thin films in dye-sensitized solar cells

Poly(N-vinyl caprolactam) (PNVCL) side chains were grafted to a poly(vinyl chloride) (PVC) backbone via atom transfer radical polymerization. The synthesized PVC-g-PNVCL graft copolymer was templated for the preparation of porous TiO₂ thin films, which involved a sol–gel reaction and calcination process. The interaction of the carbonyl groups in the PVC-g-PNVCL with the titania was revealed by FT-IR spectroscopy. X-ray diffraction and transmission electron microscopy analysis showed the formation of porous TiO₂ thin films with the anatase phase. A series of porous TiO₂ thin films with different pore sizes and porosities was prepared by varying the solution compositions and were used as photoelectrodes in dye-sensitized solar cells (DSSC) with a polymer electrolyte. The DSSC performed best when using the TiO₂ film with higher porosity, lower interfacial resistance, and longer electron life time. The highest energy conversion efficiency, photovoltage (V _oc), photocurrent density (J _sc), and fill factor (FF) were 1.2%, 0.68 V, 3.2 mA/cm², and 0.57 at 100 mW/cm², respectively, for the quasi-solid state DSSC with a 730-nm-thick TiO₂ film.     

Optical and electrical properties of nanocrystalline TiO<Subscript>2</Subscript>:Pd semiconducting oxides

Electrical and optical properties of TiO₂:Pd thin films deposited from Ti-Pd mosaic targets sputtered in reactive oxygen plasma have been studied. The properties were investigated for thin films with the Pd amount of 5.5 at. %, 8.4 at. % and 23 at. %. Based on resistivity measurements a drop from 10³ down to almost 10⁻³Ωcm has been recorded when the Pd amount was varied from 5.5 at. % to 23 at. %, respectively. Moreover, it was shown that doping with different amounts of Pd results in the possibility of obtaining both types of electrical conduction: n-type for the TiO₂ with 5.5 at. % and 8.4 at. % of Pd and p-type for the TiO₂ with 23 at. % of Pd thin films. From optical measurements it has been found that as the Pd amount was increased the transmission through the thin films was reduced and position of the fundamental absorption edge was shifted toward a longer wavelength range of up to 600 nm. The optical band gap was calculated for direct and indirect transitions from optical absorption spectra. Structural properties were characterized by X-ray diffraction (XRD) and atomic force microscopy (AFM). The XRD patterns displayed occurrence of the crystalline, TiO₂-rutile for lower Pd amounts (5.5 at. %, 8.4 at. %), while the TiO₂:Pd (23 at. %) thin films displayed XRD-amorphous behaviour. Images obtained from AFM displayed dense, nanocrystalline structure with homogenous distribution of crystallites. Additionally performed secondary ion mass spectroscopy investigation confirmed homogenous distribution of Pd in the whole thickness of the prepared thin films.     

Sensitizing of Sm<Superscript>3+</Superscript> fluorescence by silver dopant in the TiO<Subscript>2</Subscript> films

Composite material based on a TiO₂ matrix doped with Sm³⁺ ions and co-doped with silver was investigated. Samarium ions together with nano- and micro-aggregates of silver were incorporated into the titanium alkoxide during the sol-gel process. Samarium ions were excited either directly (λ _exc = 488 nm) or through the TiO₂ host (λ _exc = 355 nm). It was revealed that samarium fluorescence (λ _exc = 488 nm) in gelled TiO₂ films is enhanced by up to 20 times in the vicinity of silver inclusions. Sensitizing and plasmonic mechanisms of enhancement in Sm³⁺ fluorescence are discussed.     

Effects of LaNiO<Subscript>3</Subscript> on the structures and properties of SrBi<Subscript>2</Subscript>Ta<Subscript>2</Subscript>O<Subscript>9</Subscript> thin films

SrBi₂Ta₂O₉(SBT)/LaNiO₃(LNO)/Si and SBT/Pt/TiO₂/SiO₂/Si multilayers were fabricated by pulsed laser deposition. With Pt top electrodes, the measured remanent polarization (2P_r) of Pt/SBT/LNO/Si and Pt/SBT/Pt/TiO₂/SiO₂/Si capacitors was 6.5 C/cm² and 5.2 C/cm², respectively. Using LNO as both bottom electrodes and buffer layers, enhanced non-c-axis crystalline SBT films were induced, which resulted in a 2P_r greater than that of the Pt/SBT/Pt/TiO₂/SiO₂/Si capacitor. The hysteresis loop of the Pt/SBT/LNO/Si capacitor showed a great external-field-dependent horizontal shift. Using an electron-injection model, this dependence was addressed. The fatigue-free property of the Pt/SBT/LNO/Si capacitor was experimentally established, in that the non-volatile polarization decreased by less than 5% of the initial value after 1.44×10⁹ switching cycles . PACS 77.84.Dy; 68.65.+g     

Thermal sensors based on Sb<Subscript>2</Subscript>Te<Subscript>3</Subscript> and (Sb<Subscript>2</Subscript>Te<Subscript>3</Subscript>)<Subscript>70</Subscript>(Bi<Subscript>2</Subscript>Te<Subscript>3</Subscript>)<Subscript>30</Subscript> thin films

Thin films of Sb₂Te₃ and (Sb₂Te₃)₇₀(Bi₂Te₃)₃₀ alloy and have been deposited on precleaned glass substrate by thermal evaporation technique in a vacuum of 2?×?10^?6 Torr. The structural study was carried out by X-ray diffractometer, which shows that the films are polycrystalline in nature. The grain size, microstrain and dislocation density were determined. The Seebeck coefficient was determined as the ratio of the potential difference across the films to the temperature difference. The power factor for the (Sb₂Te₃)₇₀ (Bi₂Te₃)₃₀ and (Sb₂Te₃) is found to be 19.602 and 1.066 of the film of thickness 1,500 Å, respectively. The Van der-Pauw technique was used to measure the Hall coefficient at room temperature. The carrier concentration was calculated and the results were discussed.     

Structural and magnetic properties of Mn-doped anatase TiO<Subscript>2</Subscript> films synthesized by atomic layer deposition

Mn-doped anatase TiO₂ (Mn: 1.2, 2.4 at%) thin films were grown on Si(100) via atomic layer deposition (ALD). The synthesis utilized Ti(OCH(CH₃)₂)₄ and H₂O as ALD precursors and Mn(DPM)₃ as a dopant source. X-ray photoelectron spectroscopy measurements indicate that Mn is successfully doped in the TiO₂ matrix and reveal information about film composition and elemental chemical states. Microstructure, crystallinity, and density were investigated with scanning electron microscopy, X-ray diffraction, and X-ray reflectivity. All ALD-synthesized films exhibited room-temperature ferromagnetism; the microstructure, density, and magnetic field-dependent magnetization of the TiO₂ varied with the concentration of Mn. ALD permits precise composition and thickness control, and much higher process throughput compared to alternative techniques.     

Nonlinear dielectric response of epitaxial Ba<Subscript>0.6</Subscript>Sr<Subscript>0.4</Subscript> TiO<Subscript> 3</Subscript> thin films

Based on Landau-Devonshire (LD)-type phenomenological thermodynamic theory, the electric field dependence of the dielectric properties of tetragonal single-domain barium strontium titanate(Ba_1-xSr_xTiO₃) films on cubic substrates is theoretically investigated by taking into account the high order terms of the polarization. At room temperature, the nonlinear dielectric responses of epitaxial Ba_0.6Sr_0.4TiO₃ films are provided by adjusting the film thickness and growth temperature. The strong nonlinearity of relative dielectric constant and pyroelectric coefficient are attained around critical film thickness on MgO (69 nm) and LaAlO₃ (132 nm) substrates or critical growth temperature on MgO (337 °C) substrate with respect to epitaxy-induced lattice misfit and thermal stresses during deposition. This can be explained that small compressive stresses are effective to support high nonlinearity of dielectric constant and pyroelectric coefficient for Ba_0.6Sr_0.4TiO₃ films irrespective of whether they are on compressive substrate or tensile substrate. It is also predicted that a large tunability may be achieved by altering processing conditions, such as the film thickness and growth temperature for different substrates. Our theoretical results are in good agreement with the experimental data reported in literature.     

Elastic instability of the nano-structured state as an intrinsic probe to study the early formation stages of sol–gel derived (Pb<Subscript>1-x</Subscript>Ca<Subscript>x</Subscript>)TiO<Subscript>3</Subscript> thin films

A novel method to investigate the early formation stages of polycrystalline (Pb_1-xCa_x)TiO₃ (PCT) perovskite films by means of traditional Brillouin and micro-Brillouin spectroscopy (BS, mBS) is described in the present work. The films were prepared by chemical solution deposition (CSD) onto oxidized (100)Si substrates and treated at temperatures between 350–650 °C by rapid thermal processing (RTP). The elastic instability observed by Brillouin spectroscopy at the nano-structured state of the PCT films was used here to determine their crystallization temperatures. Coexistence of different nanocrystalline phases (e.g., pyrochlore, perovskite) in the films could also be detected by this technique. The reliability of these results is demonstrated by complementary information obtained by X-ray diffraction (XRD) and scanning force microscopy (SFM). The effects of the annealing temperature and of the Ca²⁺ content on the crystallization process of these films are also discussed. PACS 78.35.+c; 77.84.-s; 61.82.Rx     

Scalable synthesis and superior performance of TiO<Subscript>2</Subscript>-reduced graphene oxide composite anode for sodium-ion batteries

TiO₂-reduced graphene oxide (RGO) composite was synthesized via a sol-gel process and investigated as an anode material for sodium-ion batteries (SIBs). A remarkable improvement in sodium ion storage with a reversible capacity of 227 mAh g^?1 after 50 cycles at 50 mA g^?1 is achieved, compared to that (33 mAh g^?1) for TiO₂. The enhanced electrochemical performance of TiO₂-RGO composite is attributed to the larger specific surface area and better electrical conductivity of TiO₂-RGO composite. The excellent performance of TiO₂-RGO composite enables it a potential electrode material for SIBs.     

Controlling the orientation of ZnO nanorod arrays using TiO<Subscript>2</Subscript> thin film templates dip-coated by sol–gel

The oriented ZnO nanorod arrays have been synthesized on a silicon wafer that coated with TiO₂ films by aqueous chemical method. The morphologies, phase structure and the photoluminescence (PL) properties of the as-obtained product were investigated by field-emission scanning electron microscopy (FE-SEM), X-ray diffractometer (XRD), transmission electron microscope (TEM) and PL spectrum. The nanorods were about 100 nm in diameter and more than 1 μm in length, which possessed wurtzite structure with a c axis growth direction. The room-temperature PL measurement of the nanorod arrays showed strong ultraviolet emission. The effect of the crystal structure and the thickness of TiO₂ films on the morphologies of ZnO nanostructures were investigated. It was found that the rutile TiO₂ films were appropriate to the oriented growth of ZnO nanorod arrays in comparison with anatase TiO₂ films. Moreover, flakelike ZnO nanostructures were obtained with increasing the thickness of anatase TiO₂ films.     

First-principles calculations on implanted TiO<Subscript>2</Subscript> by 3d transition metal ions

3d transition metal (V, Cr and Fe) ions are implanted into TiO₂ by the method of metal ion implantation. The electronic band structures of TiO₂ films doped 3d transition metal ions have been analyzed by ab initio band calculations based on a self-consistent full-potential linearized augmented plane-wave method within the first-principle formalism. Influence of implantation on TiO₂ films is examined by the method of UV-visible spectrometry. The results of experiment and calculation show that the optical band gap of TiO₂ films is narrowed by ion implantation. The calculation shows that the 3d state of V, Cr and Fe ions plays a significant role in red shift of UV-Vis absorbance spectrum.     

Symmetry and models of single-walled TiO<Subscript>2</Subscript> nanotubes with rectangular morphology

The formalism of line symmetry groups for one-periodic (1D) nanostructures with rotohelical symmetry has been applied for symmetry analysis of single-walled titania nanotubes (SW TiO₂ NTs) formed by rolling up the stoichiometric two-periodic (2D) slabs of anatase structure. Either six- or twelve-layer (101) slabs have been cut from TiO₂ crystal in a stable anatase phase. After structural optimization, the latter keeps the centered rectangular symmetry of initial slab slightly compressed along a direction coincided with large sides of elemental rectangles. We have considered two sets of SW TiO₂ NTs with optimized six- and twelve-layer structures, which possess chiralities (−n, n) and (n, n) of anatase nanotubes. To analyze the structural and electronic properties of titania slabs and nanotubes, we have performed their ab initio LCAO calculations, using the hybrid Hartree-Fock/Kohn-Sham exchange-correlation functional PBE0. The band gaps (Δɛ _gap ) and strain energies (E _strain ) of six-layer nanotubes have been computed and analyzed as functions of NT diameter (D _NT). As to models of 12-layer SW TiO₂ NTs of both chiralities, their optimization results in structural exfoliation, i.e., the multi-walled structure should be rather formed in nanotubes with such a number of atomic layers.     

High-temperature complex impedance and modulus spectroscopic studies of doped Na<Subscript>0.5</Subscript>Bi<Subscript>0.5</Subscript>TiO<Subscript>3</Subscript>-BaTiO<Subscript>3</Subscript> ferroelectric ceramics

Lead-free Na_0.5Bi_0.5TiO₃ (NBT) and (1 ? x)Na_0.5Bi_0.5TiO₃ + xBaTiO₃ with x = 0.1 and 0.2 (where x = 0.1 and 0.2 are named as NBT1 and NBT2, respectively), (1 ? y)Na_0.5Bi_0.5TiO₃ + yBa_0.925Nd_0.05TiO₃ with y = 0.1 and 0.2 (where y = 0.1 and 0.2 are named as NBT3 and NBT4, respectively)-based relaxor ferroelectric ceramics were prepared using the sol-gel method. The crystal structure was investigated by X-ray diffraction (XRD) at room temperature (RT). The XRD patterns confirmed the presence of the rhombohedral phase in all the samples. The electrical properties of the present NBT-based samples were investigated by complex impedance and the modulus spectroscopy technique in the temperature range of RT–600 °C. The AC conductivity was found to increase with the substitution of Ba²⁺ ions to the NBT sample whereas it significantly decreased with the addition of Nd³⁺ ions. The more anion vacancies in Ba-added samples and the lower anion vacancies in Nd-added samples were found to be responsible for higher and lower conductivities, respectively.     

Response of the electrical resistivity and magnetoresistance of La<Subscript>0.67</Subscript>Ca<Subscript>0.33</Subscript>MnO<Subscript>3</Subscript> films to biaxial tensile strains

The structure, electrical resistivity, and magnetoresistance of (50-nm)La_0.67Ca_0.33MnO₃ epitaxial films grown on a [(80 nm)Ba_0.25Sr_0.75TiO₃/La_0.3Sr_0.7Al_0.65Ta_0.35O₃] substrate with a substantial positive lattice misfit have been studied. The tensile biaxial strains are shown to account for the increase in the cell volume and in the relative concentration of Mn⁺³ ions in the manganite films as compared to those for the original material (33%). The peak in the temperature dependence of the resistivity ρ of La_0.67Ca_0.33MnO₃ films was shifted by 30–35 K toward lower temperatures relative to its position in the ρ(T) graph for a manganite film grown on (001)La_0.3Sr_0.7Al_0.65Ta_0.35O₃. For T < 150 K, the temperature dependences of ρ of La_0.67Ca_0.33MnO₃/Ba_0.25Sr_0.75TiO₃/La_0.3Sr_0.7Al_0.65Ta_0.35O₃ films could be well fitted by the relation ρ = ρ₀ + ρ₁T^4.5, where ρ₀ = 0.35 mΩ cm and the coefficient ρ₁ decreases linearly with increasing magnetic field. In the temperature interval 4.2–300 K, the magnetoresistance of manganite films was within the interval 15–95% (μ₀H = 5 T).     

Ferroelectric and dielectric properties of SrBi<Subscript>4</Subscript>Ti<Subscript>4</Subscript>O<Subscript>15</Subscript> thin films grown on Bi<Subscript>4</Subscript>Ti<Subscript>3</Subscript>O<Subscript>12</Subscript> film layer

Ferroelectric and dielectric properties of bilayered ferroelectric thin films, SrBi₄Ti₄O₁₅ grown on Bi₄Ti₃O₁₂, were investigated. The thin films were annealed at 700°C under oxygen atmosphere. The bilayered thin films were prepared on a Pt(111)/Ti/SiO₂/Si substrate by a chemical solution deposition method. The dielectric constant and dielectric loss of the bilayered thin films were 645 and 0.09, respectively, at 100 kHz. The value of remnant polarization (2P _r) measured from the ferroelectric thin film capacitors was 60.5 μC/cm² at electric field of 200 kV/cm. The remnant polarization was reduced by 22% of the initial value after 10¹⁰ switching cycles. The results showed that the ferroelectric and dielectric properties of the SrBi₄Ti₄O₁₅ on Bi₄Ti₃O₁₂ ferroelectric thin films were better than those of the SrBi₄Ti₄O₁₅ grown on a Pt-coated Si substrate suggesting that the improved properties may be due to the different nucleation and growth kinetics of SrBi₄Ti₄O₁₅ on the c-axis-oriented Bi₄Ti₃O₁₂ layer or on the Pt-coated Si substrate.     

Magnetic properties of LiNi<Subscript>0.5</Subscript>Mn<Subscript>0.47</Subscript>Al<Subscript>0.03</Subscript>O<Subscript>2</Subscript> as positive electrode for Li-ion batteries

The layered LiNi_0.5Mn_0.47Al_0.03O₂ was synthesized by wet chemical method and characterized by X-ray diffraction and analysis of magnetic measurements. The powders adopted the α-NaFeO₂ structure. This substitution of Al for Mn promotes the formation of Li(Ni_0.47²⁺Ni_0.03³⁺Mn_0.47⁴⁺Al_0.03³⁺)O₂ structures and induces an increase in the average oxidation state of Ni, thereby leading to the shrinkage of the lattice unit cell. The concentration of antisite defects in which Ni²⁺ occupies the (3a) Li lattice sites in the Wyckoff notation has been estimated from the ferromagnetic Ni²⁺(3a)–Mn⁴⁺(3b) pairing observed below 140 K. The substitution of 3% Al for Mn reduces the amount of antisite defects from 7% to 6.4–6.5%. The analysis of the magnetic properties in the paramagnetic phase in the framework of the Curie–Weiss law agrees well with the combination of Ni²⁺ (S = 1), Ni³⁺ (S = 1/2) and Mn⁴⁺ (S = 3/2) spin-only values. Delithiation has been made by the use of K₂S₂O₈. According to this process, known to be softer than the electrochemical one, the nickel ions in the (3b) sites are converted into Ni⁴⁺ in the high spin configuration, while Ni²⁺(3a)–Mn⁴⁺(3b) ferromagnetic pairs remain, as the Li⁺(3b) ions linked to the Ni²⁺(3a) ions in the antisite defects are not removed. The results show that the antisite defect is surrounded by Mn⁴⁺ ions, implying the nonuniform distribution of the cations in agreement with previous NMR and neutron experiments.